DE1063302B - Process for the preparation of chloroaryl compounds - Google Patents

Description

GERMAN

Many processes are already known which involve the introduction of halogen atoms into organic compounds allow. These known methods mostly use free halogen, e.g. B. Chlorine or products like sulfuryl chloride, which behave like a mixture of sulfur dioxide and free chlorine. You own however, in many cases, significant disadvantages, for example, by the reaction on an industrial scale progresses very slowly or by the free halogen or evolving during the reaction Hydrogen halide a considerable attack on the equipment used takes place, in particular if the halogenation proceeds in the desired sense only under relatively severe conditions. It is also used because of its volatility Halogenating agent an exact dosage associated with difficulties, in many cases the must Halogenation can be kept under constant control. The halogenation products from various Approaches of the same starting material often differ from one another in terms of their composition. The usage of sulfuryl or thionyl halides in the presence of aluminum chloride is known to lead to Halogenation products with a considerable sulfur content, which, especially in the case of vat dyes, of can have an adverse effect on the properties of these dyes.

It has now been found that cyclic compounds containing ring-shaped carbonyl groups which contain at least nine, at least partially condensed aromatic six-membered rings, can advantageously be chlorinated if they are heated in an anhydrous chlorinating agent, on the one hand anhydrous aluminum chloride and on the other hand sulfur trioxide or compounds in general Formula R — SO ₂ - contains halogen, where R is one of the groups —OH, —O-metal or an organic radical.

In the present case, ring-shaped carbonyl compounds are to be understood as meaning those which have at least a carbon atom linked to an oxygen atom by a double bond as a member of a Ring, preferably an aromatic six-membered ring contain. The starting materials of the present process contain at least nine aromatic six-membered rings, and these must be at least partially either be condensed with each other or with heterocyclic rings. To prove useful z. B. such Carbonyl compounds, which exclusively ring systems with at least three fused rings and only have those with at least one carbonyl group in each ring system, i.e. starting materials that for example, do not contain any benzene or naphthalene radicals linked to other rings by a simple bond.

Process for the preparation of chloroaryl compounds

Applicant:
CIBA Aktiengesellschaft, Basel (Switzerland)

Representative: Dipl.-Ing. E. Splanemann, patent attorney, Hamburg 36, Neuer Wall 10

Claimed priority: Switzerland from May 26th and June 11th 1954

Dr. Armin Caliezi, Basel,

and Dr. Walter Kern, Sissach (Switzerland), have been named as the inventor

Otherwise, however, carbonyl compounds of various compositions can be used, see z. B. the following:

a) Carbonyl compounds, which are two benzanthrone residues contain, in particular dibenzanthrones or isodibenzanthrones.

b) Anthrimides or carbazoles with at least two - NH bridges or carbazole rings or compounds with at least two —NH bridges, some of which are simple anthrimide bridges and some of them Part as members of carbazole rings. Anthrimides and carbazoles should also be mentioned here, which condense with other rings, in particular benzene or naphthalenacridone rings! are.

c) Compounds obtained from such benzanthrones by alkaline condensation, which in the anthrone residue to at least one anthraquinonylamino group and also in the Bz-1 position a —NH-bridge tied to a linkable residue are. Such condensation products are for example in German patent 517442 described, and there are here in particular those obtainable from 6-Bz-1-di- (a-anthraquinonylamino) -benzanthrones To mention products. Furthermore, from 6-α-anthraquinonylamino-Bz-1-pyrazolanthronylbenzanthrones produced condensation products are used.

d) Anthraquinonylaminoacedianthrones, for example that of monobromoacedianthrone and 1-amirioanthraquinone available condensation product.

909 607/32 '

3 4

The starting materials listed under a) to d) can be at least 4 to 5 parts and not part of chlorosulfonic acid still others, especially in vat dyes, contain considerably more than 10 parts of anhydrous aluminum Contain substituents, e.g. B. contain low chloride.

molecular alkyl or alkoxy groups, halogen atoms, the chlorination should be carried out in an anhydrous medium

Sulfo, amino or nitro groups. Numerous at the demonstration 5.

lying process as starting materials usable The reaction temperature is among other things by this

Compounds are known and can be given that some melts at temperatures of

known methods are produced. noticeably less than 60 ^° C. only poorly or hardly at all

As compounds of the general formula R - SO ₂ - are more stirrable. A critical upper temperature halogen can, for example, be chlorosulfonic acid and io limit does not seem to exist. On the other hand will be, used in fluorosulfonic acid, and their metal salts, for example, temperatures that are much higher than 14O ⁰ C in the sodium salts. Surprisingly, in some cases, dyestuffs with poorer properties have an effect on simple organic sulfonic acid chlorides, but they are preserved. The present method is therefore that are not themselves easily chlorierbar, with particular advantage at temperatures above 70 ⁰ C, preferably Alkansulfonsäurechloride as methanesulphonyl chloride, 15 in such 85-135 ° C carried out. Which in a similar way. As a rule, the sulfur reaction time up to the practical termination of the trioxide or sulfur trioxide in larger amounts can also be used in the same way as the formula R - SO ₂ - halogen on the carbonyl, in particular Then, if the connection is in the case of chlorosulfonic acid and reaction conditions, there is the possibility that aluminum chloride is usually about 1 to 3 hours. In compounds of the above formula R —-SO ₂ - halogen, in many cases the reaction is formed after just 1 hour. practically finished.

In many cases it is advantageous to use the anhydrous. Surprisingly, the present process can

Chlorinating agents of the composition mentioned are still passed in such a way that, despite their presence, vigorously

Add substances that reduce the enamel sulfonating compounds with practically no entry

cause temperature, for example sodium chloride, of sulfur or of sulfonic acid groups in the

Sodium fluoride, calcium chloride, potassium chloride, sulfur molecule takes place. That still the sulfur trioxide

dioxide, sodium sulfite and magnesium sulfate. or the compounds of the formula R - SO ₂ - halogen

The chlorinating agent can in a simple manner by when carrying out the halogenation reaction

Contraction of the substances mentioned are obtained, 30 plays an essential role, it follows that im

whereby it can remain open in individual cases, generally per molecule R - SO ₂ - halogen or

to what extent before the chlorination reaction occurs, sulfur trioxide introduces a halogen atom into the halogen atom

a mutual reaction between the mixing compound can be introduced,

partners takes place. In many cases it is convenient to The reaction mechanism from halogenation is likely

the compound of the formula R - SO ₂ - halogen to 35 via a complex salt formation according to equations 1 and 2

to add solid or molten aluminum chloride, to be formulated; but the invention is not intended in any

since in this way the touchability of the manner is often tied to some theory.
Melt is increased. In many cases it is also possible

the compound to be chlorinated in a melt of RSO ₂ Cl + AlCl ₃ - * - [AlCl ₃ · RSO ₂ ] ⁰ Cl ©, 1

Aluminum chloride, expediently with the abovementioned 4 ° [AlCl -RSOl ⁰ Cl ⁰ 4- XH>

Substances produced, entered and the sulfur trioxide 2

or the compounds of the formula R - SO ₂ - halogen - * ■ [AlCl ₃ · RSO ₂ ] ⁰ H® + X - Cl,

to be added as the last component. Finally you can

also mix all reactants from the beginning. wherein R is one of the groups —OH, —-O-metal or

As a for the present process particularly a 45 represents an organic radical and X - H the to

A mixture of chlorinating compounds turns out to be a suitable chlorinating agent. When using

of an aluminum halide, in particular aluminum SO ₃ , the following primary reaction must be carried out:

chloride, and a halogen sulfonic acid, such as fluorine cn ιλιγι, iin ncn π ι
sulfonic acid, but especially chlorosulfonic acid.

The quantitative ratios between carbonyl compound, 50 for the further stages then apply the specified reaction

Aluminum chloride, halosulfonic acid and melting scheme.

Point-lowering additive can be used within further As in the case of the in anhydrous, liquid chlorination

Boundaries fluctuate. Depending on whether free chlorine is practical in relation to the reaction carried out in the medium

The amount of carbonyl compound used occurs more or not at all, the reaction can generally take place below

less halosulphonic acid is used, the equipment can be considerably spared,

stronger or weaker impact take place. Furthermore, it is advantageous that in many cases the ChIo-

Aluminum chloride is used with advantage at least ration is completed in 1 to 2 hours.

the weight double the amount of carbonyl compounds Another advantage of the process is that

binding, but in most cases it is recommended that the low volatility of the ChLo-

add significantly more aluminum chloride. 60 ration agents compared to the usual ones

The additives, which lower the melting point, allow precise dosing of the amount of chlorination agents, see above

moderately in a manner known per se that uniform chlorination results are obtained.

Adapted to aluminum chloride. Simpler apparatus can also be used

In order for the melt to be the one for the present, and finally the process in many

Process favorable temperatures sufficiently thin - 65 cases work at lower temperatures than this

remains liquid and easy to stir, are necessary to 1 mol with the common chlorinating agents

Halosulfonic acid with advantage at least 1 mol, is useful.

moderately but much more, z. B. about 8 moles of aluminum- If the molecule of the present process

halide used. Advantageous results are created in the substance to be chlorinated so that a z. B.

some cases obtained with mixtures that point to a 7 ° intramolecular condensation or some other type of condensation

5 6

Inclusion, e.g. a carbazolation, is possible, so 87 to 90 ° 5 parts of dibenzanthrone and leaves the mixture such a condensation or such a ring can stir for 1 hour at 87 to 90 °. Then the melt Finally, in addition to the chlorination reaction, in many cases poured onto ice and water, acidic to the Congo with hydrochloric acid be effected. placed, heated to 90 °, filtered, the residue neutral

The products obtained are generally 5 washed and dried.

valuable vat dyes or can, if they, as obtained about 6.1 parts of a blue-black powder,

z. B. certain anthrimides, in and of themselves today's cotton in strong, pure, violet-blue tones with high requirements in terms of vatting, draw- dyes of good fastness properties. The chlorine content of a product obtained in this way or no longer in fastness properties was 20 ° / _Q.
correspond to the full extent, in such valuable io.

Vat dyes are transferred (e.g. by Carba example I

zolation of the anthrimides). The vat dyes can be a mixture of 400 parts anhydrous aluminum Customary for dyeing and printing the chlorid, 65 parts of sodium chloride, 4 parts of sodium separates Materials used, especially fluoride, are heated to 200 ° until homogeneous for dyeing and printing cellulosic fibers, how 15 melt was created. This is lowered to 98 ° Cotton, Artificial silk and rayon from regenerated cool and gives 50 parts in the course of 40 minutes Cellulose. The colorations obtained have chlorosulfonic acid added in many and then in 20 minutes Cases a particularly good fastness to chlorine. Compared to 50 parts of the starting dyes according to Example 1 of the German patent and known products that are made from font 517 442 by alkaline condensation these starting dyes obtained with such agents 20 6, Bz-l-di- (a-anthraquinonylamino) -benzanthrone hergewerden, which, in addition to halogenation, also represents the dye. After completing the entry, the Cause entry of sulfur, for example, stirred and mixed for 1 hour at 98 to 103 ° compared to the mixture the dyes which are obtained if the worked up as in Example 1. The yield is when exposed to alkaline condensation - about 56.6 parts.

average to 6, Bz-l-di- (a-anthraquinonylamino) -benz- 25 The dye is a black-green powder and colors anthrone products according to German patent cotton in pure, olive tones of excellent font 743 592 a treatment with thionyl chloride fastness properties . It contains about 16.6% chlorine,
and aluminum chloride subjects, the will only stand out in half the amount given above

corresponding end products of the present process chlorosulphonic acid used (25 parts), one obtains a through better coloring properties. 30 product having a chlorine content of about 9.8 ° / _0th

From the reports of the German Chemical Society. .

schaft, Vol. 60 (1927), p. 577, it is known that AlCl _{3 is} based on Example 6

Perylene in the presence of oxidizing agents hihalogenating A mixture of 100 parts of anhydrous aluminum has an effect. However, compared to the chloride, this process has 16 parts of sodium chloride and 20 parts of chlorine according to the invention the following disadvantages: 35 sulfonic acid is heated to 120 ° until it is easily stirrable

a) Manganese dioxide must have arisen from the reaction product through melting. Then leave the temperature a special operation can be removed (reduction). the melt will drop to 90 ° and contribute at 90 to 92 °

b) During the chlorination, chlorine gas is released, whereby 10 parts of the according to Example 1 of the German patent increased corrosion of the equipment occurs. 517 442 by alkaline condensation from 6, Bz-I-Di-

c) The chlorination is less effective than the color claims produced by 40 (a-anthraquinonylamino) -benzanthrone Method, as one substance per mole of aluminum chloride. The mixture is then left for 1 hour less chlorine stirred into the compound to be chlorinated at 90 to 92 ° and worked up as in Example 1, is introduced. About 12.4 parts are obtained.

U.S. Patents 2,698,347 and 2,698,348 The dye stains similarly to that of Example 2.

describe processes for the production of halogen 45 Its chlorine content is about 21.6%.
hydrocarbons by removing the gaseous hydrocarbons. .

Hydrogen at 250 to 45O ⁰ C, together with sulfur Example 4

trioxide through a reaction zone of alkali or earth A mixture of 80 parts of aluminum chloride,

alkali halides are passed. 13 parts of sodium chloride and 10 parts of chlorosulfonic acid also avoid working with free chlorine, but 5 ° can only be used for volatile compounds by introducing a stream of sulfur dioxide. 88 ° liquefied. Then add at the same temperature. In addition, the degree of halogenation is difficult to dose 10 parts of that according to Example 1 of the German patent, and only part of the 517 442 used is halogenated by alkaline condensation from 6, Bz-I-di-hydrocarbons. In contrast, (a-anthraquinonylamino) -benzanthrone produced color the present process has the advantage, especially for 55 substances added and the mixture is stirred for 1 hour at 88 high molecular weight, non-volatile compounds applicable up to 89 °. The work-up takes place as to be in Example 1 and practically uniform products from the specified,
to provide the desired degree of halogenation. About 10.9 parts of one similar to that are obtained

In the following examples, the parts of Example 2 denote a coloring dye. Its chlorine content, unless otherwise noted, parts by weight, which is 60, is about 14.5%.
Percentages are percentages by weight, and temperatures are. .

given in degrees Celsius. Example 5

. In a melt of 80 parts of aluminum chloride,

Example 1 _{13 parts of} sodium chloride and 0.8 part of sodium fluoride

A mixture of 80 parts of anhydrous aluminum 65 is carried at 120 ° 10 parts of that used in Example 2 chloride, 13 parts of sodium chloride and 0.8 part of sodium starting product and stirred for 1 hour at 120 bis fluoride is heated to 150 ° until a uniform 125 ° until the carbazolation has ended. Then cool Melt has arisen. This is reduced to 90 °, the melt is reduced to 100 °, and 12 parts of chlorosulfone are added and add acidic sodium dropwise at this temperature and stir the melt another 5 parts of chlorosulfonic acid are added. Then wear at 95 to 100 ° for 70 hours. Receives after work-up

7 8

a vat dye, the cotton in a bluish tint. Example 12

dyes olive shades of very good fastness properties. Its 80 parts aluminum chloride, 13 parts sodium chloride,

Chlorine content is around 12%. 0.8 parts of sodium fluoride and 10 parts of chlorosulfonic acid

. . are heated to 140 ° until a clear melt is formed.

Example 6 5 stood. This is cooled to 100 ° and 10 parts are given

In a melt of 80 parts of aluminum chloride, plus isodibenzanthrone. You keep the temperature 13 parts of sodium chloride and 0.8 parts of sodium fluoride for 1 hour at 98 to 103 ° and works as in Example 1 one leaves at 90 to 95 ° 4.2 parts of methanesulfonyl chloride indicated on. The product obtained contains about drop and then carries 5 parts of the chlorine in Example 2 22%.

used starting product. This is followed by example 13

the melt 45 minutes at 90 to 95 ° and works it,

as indicated in Example 1 on. The product contains If one uses in Example 12 instead of Isodibenz-

about 13% chlorine and shows similar dyeing eigen- anthrones to those according to example 1 of the German patents like the dye obtained according to Example 2. 520 395 by alkaline condensation . 15 Anthraquinonylamino-Bz-1-benzanthronyl-Py-l-pyrazole-

Example 7 anthrone-made dye, a product is obtained

A mixture of 80 parts of aluminum chloride, which dyes cotton in a bluish olive and 16 parts of sodium chloride, 0.8 parts of sodium fluoride and a chlorine content of about 17.5%.
11 parts of oleum (66%) are heated to 140 ° until one. .

homogeneous melt has arisen. This is cooled to ao example 14

100 ° and carries 10 parts of the German Example 1 A mixture of 80 parts of aluminum chloride,

Patent 517442 by alkaline condensation 13 parts of sodium chloride, 0.8 parts of sodium fluoride and from 6, Bz-l-di- (a-anthraquinonylamino) -benzanthronher- 5 parts of fluorosulfonic acid is heated to 140 ° for so long set dye. The melt is stirred until a clear melt has formed. To this one gives 1 hour at 98 to 103 ° and works it up as usual. 25 after cooling to 100 ° 5 parts isodibenzanthrone and A sulfur-free vat dye is obtained by heating the mixture to 98-103 ° for 1 hour. After Chlorine content of about 17%, which is yellow on cotton. Work-up gives cotton a purple color pungent olive dyes with excellent fastness properties. Product that contains approximately 22% chlorine.

. . Used in place of isodibenzanthrone

.Example ^ ₀ ]) ib _enzan thxon, is a chlorine-containing cotton in

If, in Example 7, a blue-violet tone coloring dye is obtained instead of oleum.
11.9 parts of sodium chlorosulfonate are obtained. .

Product of similar characteristics. Example 15

. -in to a melt of 120 parts of aluminum chloride,

Example 9 35 40 parts of titanium tetrachloride, 20 parts of sodium fluoride

A mixture of 100 parts of aluminum chloride and 20 parts of chlorosulphonic acid is added at 120 ° to 20 parts of 40 parts of chlorosulphonic acid and heated to 160 ° of the starting material used in Example 2 for 3 hours. Then the melt is cooled to 100 ° and the mixture for 1 hour at 100 to 120 ° and carries it on carries 10 parts of the according to Example 1 of the German patent from so much ice that the temperature of the aqueous solution font 517 442 by alkaline Condensation from 40 never exceeds 20 °. The mixture is acidified with salt-6, Bz-1-di- (a-anthraquinonylamino) -benzanthrone and stirred for 1 hour at 0 ° to 20 °. Then the dye is set. The mixture is heated to 120 ° and the dye is filtered off, washed neutral and stirred and stirred at this temperature for 1 hour. After dries. It contains about 16% chlorine and colors the tree.
Get chlorine content of around 20%, the cotton in 45
pure olive tones with excellent fastness properties
colors. To a melt of 80 parts of aluminum chloride,

Example 10 parts of sodium chloride and 10 parts of chlorosulfonic acid

are given at 100 ° 10 parts of the condensation of

To a melt of 80 parts of aluminum chloride 50 1 mol of tetrabromopyranthrone with 3 ^× / ₂ mol of aminodibenz-13 parts of sodium chloride, 0.8 part of sodium fluoride and anthrone and ^× / ₂ mol of a-amino-anthraquinone, 5 parts of fluorosulfonic acid are added at 100.degree Parts of the black dye and the whole is stirred for 1 hour with the starting product used in Example 2 and stirred at 98 to 103 °. The product obtained has a chlorine melt for 1 hour at 98-103 °. After the content of about 25% and dyes cotton in a gray finish, an olive-dyed vat color is obtained.

substance of similar properties to that of Example 2. Example 17

received. .

Beismelll ^ ^ue ^ ^ner melt from 100 parts of aluminum chloride,

20 parts of sodium chloride, 1 part of sodium fluoride and

5 parts of 13 parts of sodium chloride and 0.8 parts of sodium fluoride are added at 90 ° to a melt of 80 parts of aluminum chloride and 60 17 parts of chlorosulfonic acid by condensation of 4,4'-diamino-1,1'-dianthrimide 5 parts of methanesulfonyl chloride and then tetraanthrone obtained with 2 moles of 1-chloro-anthraquinone, 5 parts of dibenzanthrone. Then the mids and keeps the temperature at 90 ° for 3 hours. Then, the melt was stirred further 1 hour at 90 to 95 ° and how the melt is heated to 120 ° undhältsie2 _^half hours worked up as usual. A violet-blue coloring 65 is obtained at this temperature. The product obtained after the usual up-product, which is about 3 atoms of chlorine per mole of dibenzanthrone work, has about 28% chlorine. contains. . .

Lo a similar example of cotton in a slightly purple shade

coloring product is obtained when using To a melt of 100 parts of aluminum chloride,

Isodibenzanthrone. 70 20 parts of sodium chloride, 1 part of sodium fluoride and

9 parts of chlorosulfonic acid are added at 90 ° to 5 parts of the by condensation of i ^ '- diamino-ljl'-dianthrimide carbazal with 2 mol of 1-chloro-anthraquinone obtained tetraanthrimide monocarbazals, then heated the whole thing within 2 hours to 120 ° and holds this temperature for 1 hour. Then the temperature of the melt increased to 160 ° and held at 160 to 162 ° for 1 hour. After the work-up one receives one Vat dye that dyes cotton gray and has a chlorine content of around 23%.

Example 19

In a melt of 200 parts of aluminum chloride, 40 parts of sodium chloride, 2 parts of sodium fluoride and 18 parts of chlorosulfonic acid are added at 90 ° to 10 parts of l, 4, r, l "-trianthrimide carbazole (cf. German patent specification 451 495) and heated the whole thing for 3 hours to 90 °, 1 hour to 120 ° and 1 hour to 140 °. After Working up gives a product which contains about 26% chlorine.

Example 20

In a melt of 150 parts of aluminum chloride, 30 parts of sodium chloride, 1.5 parts of sodium fluoride and 7.6 parts of chlorosulfonic acid are added at 100 ° to 7 parts of the carbazolation with aluminum chloride and Pyridine obtained from the starting product of Example 18 tetraanthrimide carbazole. Then you increase the temperature in the course of 6 hours to 160 °, stirred for 1 hour at 160 ° and carries the melt on ice and Water out. After working up, a gray vat dye with a chlorine content of approx 21%

Example 21

3 parts of the pentaanthrimide carbazole obtained according to Example 1 of German Patent 821386 are at 100 to 120 ° in a melt of 50 parts of aluminum chloride, 10 parts of sodium chloride, 0.5 parts Sodium fluoride and 5.2 parts of chlorosulfonic acid treated for 1 hour lsng. A gray vat dye is obtained, which contains about 14% chlorine. "

Example 22

In a melt of 30 parts of aluminum chloride, 6 parts of sodium chloride, 0.3 parts of sodium fluoride and 1.3 parts of chlorosulfonic acid are added to 1 part of the condensation product from 1 mol of 2,7-dichloroanthraquinone at 90 ° and 2 moles of amino-acedianthrone and heats it up

A full 30 minutes at 100 ° and 30 minutes at 120 °. After the usual work-up, a brown one is obtained Vat dye, which contains about 22% chlorine.

Claims (7)

Patent claims: 1. A process for the preparation of chloraryl compounds, characterized in that ring-shaped Carbonyl compounds, which are at least nine, at least partially condensed aromatic Containing six rings, heated in an anhydrous chlorinating agent, the one hand anhydrous Aluminum chloride and, on the other hand, sulfur trioxide or compounds of the general formula R-SO ₂ halogen contains, where R is one of the groups - OH, - O-metal or means an organic radical. 2. The method according to claim 1, characterized by the use of chlorosulfonic acid. 3. The method according to any one of claims 1 and 2, characterized in that one is in the presence Melting point lowering agents, in particular inorganic melting point lowering agents, is working. 4. The method according to any one of claims 1 to 3, characterized in that there is 1 mol of halosulfonic acid at least 1 mole of aluminum halide is used. 5. The method according to any one of claims 1 to 4, characterized in that the reaction at Temperatures above 60 ° C, expediently between 85 and 135 ° C carried out. 6. The method according to any one of claims 1 to 5, characterized in that such carbonyl compounds used as starting materials, which exclusively ring systems with at least three have fused rings and ring systems containing at least one carbonyl group as a ring member. 7. The method according to claim 6, characterized in that such carbonyl compounds which contain two benzanthrone residues as starting materials used. Considered publications:
U.S. Patent Nos. 2,698,347, 2,698,348;
Reports of the German Chemical Society, Vol. 60 (1927), pp. 577 to 581. A coloring table was displayed when the application was announced.